Method for the trichromatic dyeing or printing of synthetic polyamide fibre materials

ABSTRACT

Method for the trichromatic dyeing or printing of synthetic polyamide fiber material, wherein at least one red reactive dye of formula  
                 
 
     is used together with at least one of the yellow or orange reactive dyes of formulae  
                 
 
     and at least one blue reactive dye of formula  
                 
 
     in which formulae  
     the variables are as defined in claim  1,    
     which method is distinguished by a uniform color build-up and a very good combinability.

[0001] The present invention relates to a method of trichromatic dyeingor printing and to the red reactive dyes especially suitable for thatpurpose.

[0002] The problem underlying the present invention was to find a methodof dyeing or printing synthetic polyamide fibre materials, for examplewoven carpet fabrics, using reactive dyes suitable for combinationaccording to the trichromatic principle.

[0003] It has now been found that the problem can be solved according tothe invention by the method described hereinbelow. The dyeings soobtained meet the set objectives in a special manner. The dyeingsobtained are distinguished especially by uniform colour build-up and, atthe same time, constancy of shade at different concentrations, and bygood combinability, and exhibit good fibre levelness and no dichroism.

[0004] The present invention accordingly relates to a method for thetrichromatic dyeing or printing of synthetic polyamide fibre material inwhich at least one red reactive dye of formula

[0005] is used together with at least one of the yellow or orangereactive dyes of formulae

[0006] and at least one blue reactive dye of formula

[0007] in which formulae

[0008] R₁, R₄, R₆, R₁₀, R₁₅ and R₁₆ are each independently of the othershydrogen, or C₁-C₄alkyl unsubstituted or substituted by hydroxy, sulfo,sulfato, carboxy or by cyano,

[0009] R₂, R₅, R₇, R₁₃ and R₁₄ are each independently of the othershydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, ureido,sulfamoyl, halogen, sulfo or carboxy,

[0010] R₃ is amino or N-mono- or N,N-di-C₁-C₄alkylamino,

[0011] R₈ is hydrogen, sulfomethyl, carbamoyl or cyano,

[0012] R₉ is C₁-C₄alkyl,

[0013] R₁₁, and R₁₂ are each independently of the other hydrogen,C₁-C₄alkyl, C₁-C₄alkoxy, halogen, sulfo or carboxy,

[0014] B is a C₂-C₆alkylene radical, which may be interrupted by 1, 2 or3 —O— members and which is unsubstituted or substituted by hydroxy or bysulfato, or

[0015] a cyclohexylene radical or methylene-cyclohexylene radical eachof which is unsubstituted or substituted by C₁-C₄alkyl, or

[0016] a phenylene or methylene-phenylene-methylene radical each ofwhich is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,halogen or by sulfo,

[0017] I is the number 0 or 1,

[0018] k is the number 1, 2 or 3, and

[0019] V₁ is a radical of formula

[0020]  in which formulae

[0021] R₁₇ and R₁₉ are each independently of the other hydrogen, orC₁-C₄alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato,carboxy or by cyano,

[0022] R₁₈ is C₁-C₄alkyl, C₁-C₄alkoxy, halogen or sulfo,

[0023] Z is the radical —CH═CH₂ or —CH₂—CH₂—Y and Y is a leaving group,

[0024] m is the number 0, 1 or 2,

[0025] n is the number 0 or 1, and

[0026] V₂, V₃, V₄ und V₅ are each independently of the others a radicalof the above-indicated formula (6a), (6b), (6c) or (6d) or a radical offormula

[0027]  wherein

[0028] R₂₀ is hydrogen, or C₁-C₄alkyl unsubstituted or substituted byhydroxy, sulfo, sulfato, carboxy or by cyano, and

[0029] X is a radical

[0030]  and Hal or and Hal is bromine or chlorine,

[0031] with the proviso that

[0032] the dye of formula (1) contains two sulfo groups.

[0033] The radicals R₁, R₄, R₆, R₁₀, R₁₅, R₁₆, R₁₇, R₁₉ and R₂₀ as alkylradicals are straight chain or branched. The alkyl radicals may in turnbe substituted by hydroxy, sulfo, sulfato, cyano or by carboxy. Examplesthat may be mentioned are methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl and tert-butyl, and the corresponding radicalssubstituted by hydroxy, sulfo, sulfato, cyano or by carboxy. Preferredsubstituents are hydroxy, sulfo or sulfato, especially hydroxy orsulfato and more especially hydroxy.

[0034] According to one interesting embodiment, when B is aC₂-C₆alkylene radical that may be interrupted by 1, 2 or 3 —O— membersand is unsubstituted or substituted by hydroxy or by sulfato, one of theradicals R₁₅ and R₁₆ is C₁-C₄alkyl substituted by hydroxy, sulfo,sulfato, cyano or by carboxy and the other of the radicals R₁₅ and R₁₆is hydrogen or C₁-C₄alkyl, especially hydrogen.

[0035] C₁-C₄Alkyl radicals that come into consideration for R₂, R₅, R₇,R₁₁, R₁₂, R₁₃, R₁₄ and R₁₈, each independently of the others, are, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl and isobutyl, preferably methyl and ethyl and especiallymethyl.

[0036] R₉ as C₁-C₄alkyl is, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl, preferably methylor ethyl and especially ethyl.

[0037] C₁-C₄Alkoxy radicals that come into consideration for R₂, R₅, R₇,R₁₁, R₁₂, R₁₃, R₁₄ and R₁₈, each independently of the others, are, forexample, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy and isobutoxy, preferably methoxy and ethoxy, and especiallymethoxy.

[0038] C₂-C₄Alkanoylamino radicals that come into consideration for R₂,R₅, R₇, R₁₃ and R₁₄, each independently of the others, are, for example,acetylamino and propionylamino and especially acetylamino.

[0039] Halogen atoms that come into consideration for R₂, R₅, R₇, R₁₁,R₁₂, R₁₃, R₁₄ and R₁₈each independently of the others, are, for example,fluorine, chlorine and bromine, preferably chlorine and bromine, andespecially chlorine.

[0040] N-mono- and N,N-di-C₁-C₄alkylamino radicals that come intoconsideration for R₃, are, for example, methylamino, ethylamino,n-propylamino, n-butylamino, N,N-dimethylamino and N,N-diethylamino,preferably methylamino, ethylamino, N,N-dimethylamino andN,N-diethylamino, and especially methylamino, ethylamino andN,N-dimethylamino.

[0041] For B denoting a cyclohexylene radical or methylene-cyclohexyleneradical each of which is unsubstituted or substituted by C₁-C₄alkyl, ordenoting a phenylene or methylene-phenylene-methylene radical each ofwhich is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,halogen or by sulfo, there come into consideration as C₁-C₄alkyl,C₁-C₄alkoxy and halogen, for example, the radicals and their preferredmeanings indicated above for R₂, R₅, R₇, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₈.

[0042] The leaving group Y is, for example —Cl, —Br, —F, —OSO₃H, —SSO₃H,—OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂.Y is preferably a group of formula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃,—OCO—C₆H₅ or —OPO₃H₂, especially —Cl, —OSO₃H or —OCO—CH₃ and moreespecially —Cl or —OSO₃H.

[0043] R₁, R₄, R₆, R₁₀, R₁₅, R₁₆, R₁₇, R₁₉ and R₂₀ are preferably, eachindependently of the others, hydrogen or C₁-C₄alkyl, especiallyhydrogen, methyl or ethyl.

[0044] R₁, R₄, R₆, R₁₀, R₁₅, R₁₆, R₁₇, R₁₉ and R₂₀ are especiallypreferably hydrogen.

[0045] Preferably, R₂, R₅, R₇, R₁₃ and R₁₄ are each independently of theothers hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, ureido,sulfo or carboxy, especially hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, ureido or sulfo, and R₁₁ and R₁₂ are eachindependently of the other hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or sulfo,especially hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy.

[0046] Especially preferably, R₂ is sulfo, R₅ is ureido orC₂-C₄alkanoylamino, especially ureido, and R₇, R₁₁, R₁₂, R₁₃ and R₁₄ arehydrogen.

[0047] R₃ is preferably amino.

[0048] R₈ is preferably hydrogen, sulfomethyl or carbamoyl, especiallyhydrogen or sulfomethyl and more especially hydrogen.

[0049] B is preferably a C₂-C₆alkylene radical, amethylene-cyclohexylene radical unsubstituted or substituted byC₁-C₄alkyl, or a phenylene or methylene-phenylene-methylene radical eachof which is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,halogen or by sulfo.

[0050] B is especially preferably a radical of formula

[0051] especially of formula

[0052] R₁₈ is preferably methyl, methoxy or sulfo, especially methyl ormethoxy.

[0053] Z is preferably the radical —CH═CH₂.

[0054] V₁, V2, V3, V₄ und V₅ are preferably, each independently of theothers, a radical of formula (6c) or (6d), wherein R₁₇, R₁₈, R₁₉, Z, mund n have the meanings and preferred meanings indicated above.

[0055] I is preferably the number 0.

[0056] k is preferably the number 2 or 3, especially 3.

[0057] A suitable naphthyl radical in the dye of formula (4) ispreferably a radical of formula

[0058] m is preferably the number 0.

[0059] n is preferably the number 0.

[0060] Hal is preferably bromine.

[0061] The radical of formula (6c) is preferably a radical of formula

[0062] wherein Z has the meanings and preferred meanings given above.

[0063] The radical of formula (6d) ist preferably a radical of formula

[0064] wherein Z has the meanings and preferred meanings given above.

[0065] Preference is given to the method according to the invention inwhich, in the reactive dye of formula (1),

[0066] R₁ is hydrogen, R₂ is sulfo, R₃ is amino, I is the number 0 andV₁ is a radical of formula (6c) wherein R₁₇ is hydrogen, Z is vinyl andm is the number 0.

[0067] Special preference is given to the method according to theinvention in which the reactive dye of formula (1) is a reactive dye

[0068] Preference is given to the method according to the invention inwhich, in the reactive dye of formula (2),

[0069] R₄ is hydrogen, R₅ is ureido and V₂ is a radical of formula (6c)wherein R₁₇ is hydrogen, Z is vinyl and m is the number 0.

[0070] Preference is given to the method according to the invention inwhich, in the reactive dye of formula (3),

[0071] R₆, R₇ and R₈ are hydrogen, R₉ is ethyl and V₃ is a radical offormula (6c) wherein R₁₇ is hydrogen, Z is vinyl and m is the number 0.

[0072] Preference is given to the method according to the invention inwhich, in the reactive dye of formula (4),

[0073] R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are hydrogen, V₄ is a radical offormula (6d) wherein R₁₉ is hydrogen, Z is vinyl and n is the number 0,and k is the number 3.

[0074] Preference is given to the method according to the invention inwhich, in the reactive dye of formula (5),

[0075] R₁₅ and R₁₆ are hydrogen, B is a radical of the above formula(7a) or (7b), preferably of formula (7b), and V₅ is a radical of formula(6d) wherein R₁₉ is hydrogen, Z is vinyl and n is the number 0.

[0076] A suitable yellow or orange reactive dye for the method accordingto the invention is preferably a dye of formula (3) or (4), especiallyof formula (4), in which the variables have the meanings and preferredmeanings indicated hereinabove.

[0077] The reactive dyes of formulae (1), (2), (3), (4) and (5) areknown or can be prepared in analogy to known compounds.

[0078] The present invention relates also to the novel reactive dyes offormula

[0079] wherein

[0080] R₁, R₁₇ and Z have the meanings and preferred meanings indicatedhereinabove.

[0081] The reactive dye of formula (1b) is obtained, for example, byreacting the compounds of formulae

[0082] in which formulae

[0083] R₁, R₁₇ and Y have the meanings and preferred meanings givenhereinabove and Y is especially sulfato, with cyanuric chloride,followed, where appropriate, by an elimination reaction.

[0084] The individual process steps indicated above can be carried outin different orders or, in some instances, simultaneously, and sovarious process variants are possible. The reaction is generally carriedout stepwise, the order in which the single reactions between theindividual reaction components are carried out advantageously beinggeared to the particular conditions. For example, a compound of formula(9) is reacted with cyanuric chloride and the resulting product is thencondensed with a compound of formula (10). Preferably, a compound offormula (10) is reacted with cyanuric chloride and the resulting productis then condensed with a compound of formula (9).

[0085] The individual condensation reactions are carried out, forexample, according to methods known per se, usually in aqueous solution,at a temperature of, for example, from 0 to 50° C., especially from 0 to10° C., and a pH value of, for example, from 3 to 10, especially from 3to 7.

[0086] In addition, an elimination reaction may be carried out after thesynthesis. For example, reactive dyes of formula (1b) that containsulfatoethylsulfonyl radicals can be treated with a base, for examplesodium hydroxide, the sulfatoethylsulfonyl radicals being converted intovinylsulfonyl radicals.

[0087] The compounds of formulae (9) and (10) are known or can beprepared in analogy to known compounds.

[0088] The reactive dyes used in the trichromatic dyeing or printingmethod according to the invention and the reactive dyes of formula (1b)according to the invention are present either in their free sulfonicacid form or, preferably, in the form of a salt thereof.

[0089] Suitable salts are, for example, alkali metal, alkaline earthmetal or ammonium salts or salts of an organic amine. Examples that maybe mentioned are sodium, lithium, potassium or ammonium salts or amono-, di- or tri-ethanolamine salt.

[0090] The reactive dyes used in the method according to the inventionand the reactive dyes of formula (1b) according to the invention maycomprise further additives, for example sodium chloride or dextrin.

[0091] The trichromatic dyeing or printing method according to theinvention and the reactive dyes of formula (1b) according to theinvention can be utilised in the customary dyeing and printing methods.The dye liquors or printing pastes, in addition to comprising water andthe dyes, may comprise further additives, for example wetting agents,antifoams, levelling agents or agents that influence the characteristicsof the textile material, for example softeners, flame-retardantadditives, or dirt-, water- and oil-repellents, and also water-softenersand natural or synthetic thickeners, for example alginates and celluloseethers.

[0092] The amounts in which the individual dyes are used in the dyebaths or printing pastes can vary within wide limits depending on therequired depth of shade; in general, amounts of from 0.01 to 15% byweight, especially from 0.1 to 10% by weight, based on the material tobe dyed and the printing paste have proved to be advantageous.

[0093] In the case of woven carpet fabrics, printing methods such as,for example, displacement printing or space dyeing are important.

[0094] Preference is given to dyeing, which is carried out especially bythe exhaust process and, in the case of carpet dyeing, can also becarried out in accordance with the continuous process.

[0095] Dyeing is preferably carried out at a pH of from 2 to 7,especially from 2.5 to 5.5 and more especially from 2.5 to 4. The liquorratio can be selected within a wide range, for example from 1:5 to 1:50,preferably from 1:5 to 1:30. Dyeing is preferably carried out at atemperature of from 80 to 130° C., especially from 85 to 120° C.

[0096] To increase the fastness to wetting properties, any unfixed dyecan be removed by an aftertreatment at a pH value of, for example, from7 to 12, especially from 7 to 9, and at a temperature of, for example,from 30 to 100° C., especially from 50 to 80° C. Advantageously, in thecase of intense colour shades, for example very deep dyeings, especiallyon fibre blends, the unfixed dye can be removed reductively by theaddition of a reducing agent, for example hydrosulfite, such as sodiumhydrosulfite, to the alkaline aftertreatment bath. The dye fixed in thepolyamide fibre material is not affected by the treatment. The reducingagent is advantageously added in an amount of, for example, from 0.1 to6% by weight, especially from 0.5 to 5% by weight, based on the weightof the aftertreatment bath.

[0097] When employed in trichromatic dyeing or printing, the reactivedyes used in the method according to the invention and the reactive dyesof formula (1b) according to the invention are distinguished by uniformcolour build-up, good pick-up and fixing characteristics, good constancyof shade even at different concentrations, good fastness properties and,especially, by very good combinability.

[0098] The trichromatic method according to the invention and thereactive dyes of formula (1b) according to the invention are suitablefor dyeing or printing synthetic polyamide fibre materials, such as, forexample, polyamide 6 (poly-ε-caprolactam), polyamide 6.6(polyhexamethyleneadipic amide), polyamide 7, polyamide 6.12(polyhexamethylenedodecanoic amide), polyamide 11 or polyamide 12,copolyamides with polyamide 6.6 or polyamide 6, for example polymers ofhexamethylenediamine, F-caprolactam and adipic acid and polymers ofadipic acid, hexamethylenediamine and isophthalic acid or of adipicacid, hexamethylenediamine and 2-methylpentamethylenediamine or2-ethyltetramethylenediamine, and are also suitable for dyeing orprinting blended fabrics or yarns of synthetic polyamide and wool.

[0099] The method according to the invention and the reactive dyesaccording to the invention are advantageously also suitable for dyeingor printing microfibres of synthetic polyamides. Microfibres are to beunderstood as fibre materials that are composed of threads having anindividual thread fineness of less than 1 denier (1.1 dTex). Suchmicrofibres are known and are usually produced by melt-spinning

[0100] The reactive dyes of formula (1b) according to the invention arealso suitable for dyeing or printing natural polyamide fibre materials,for example wool or silk, especially wool and wool having amachine-wash-resistant finish.

[0101] The dyeing or printing of synthetic polyamide fibre materials ispreferred.

[0102] The said textile material can be in a very wide variety ofprocessing forms, for example in the form of fibres, yarn, woven fabric,knitted fabric and in the form of carpets.

[0103] Level dyeings having good all-round fastness properties,especially good fastness to rubbing, to wetting, to wet rubbing and tolight, are obtained.

[0104] In the Examples that follow, parts indicate parts by weight. Thetemperatures are in degrees Celsius. The relationship between parts byweight and parts by volume is the same as that between grams and cubiccentimeters.

PREPARATION EXAMPLE 1

[0105] a) 7 parts of a compound that in free acid form corresponds toformula

[0106] are stirred in 100 parts of water, adjusted to pH 6 by theaddition of 0.35 part of Na₂HPO₄.12H₂O and cooled to a temperature of 0°C. A solution of 4.85 parts of cyanuric chloride and 50 parts of acetoneis added dropwise in the course of from 10 to 15 minutes to thesuspension so obtained, the pH being maintained at 3 by the addition ofaqueous sodium hydroxide solution. Stirring is then carried out for onehour at a temperature of from 0 to 2° C. and a pH value of 3. After theaddition of sodium chloride, stirring is continued for a further hour.

[0107] b) 7.5 parts of a compound that in free acid form corresponds toformula

[0108] are dissolved in 100 parts of water and 11.1 parts of 1N sodiumhydroxide solution at room temperature and a pH value of 5.5. Theresulting solution is then added dropwise in the course of 45 minutes tothe solution obtained according to a). During the addition, the pH ismaintained at a value of from 5.8 to 6 by the addition of aqueous sodiumhydrogen carbonate solution. Stirring is carried out for 90 minutes atroom temperature and a pH value of from 5.8 to 6. The dye is thenfiltered off, subsequently washed with aqueous 10% sodium chloridesolution and dried at a temperature of from 30 to 35° C.

[0109] c) In order to convert the dye obtained according to b) into thevinylsulfone form, an aqueous solution of the dye is adjusted to pH 10using trisodium phosphate and stirred for 30 minutes at roomtemperature. The pH is monitored continuously and corrected wherenecessary. The end of the reaction is indicated when the pH remainsconstant. A dye is obtained that in free acid form corresponds to thecompound of formula

[0110] The dye of formula (101) dyes wool, silk and synthetic polyamidefibre material in red colour shades.

Method Example 1

[0111] A polyamide 6.6 woven carpet fabric is continuously dyed from adyebath containing, per 1000 parts of dye bath,

[0112] 0.28 part of the red dye of formula

[0113] 0.8 part of the yellow dye of formula

[0114] 0.46 part of the blue dye of formula

[0115] and also 1.0 part of a customary commercial thickener, 3.0 partsof a customary commercial antifreeze, 1.0 part of a non-ionic wettingagent, and sufficient citric acid to render the dye bath pH 5.5. Thewoven carpet fabric is then fixed in steam for 5 minutes at 100° C.,washed in the usual manner and dried. The woven carpet fabric isdistinguished by a uniform dark-brown dyeing having good fastnessproperties.

Method Examples 2 and 3

[0116] By proceeding as indicated in Example 1 but, instead of using0.28 part of the red dye of formula (101), 0.8 part of the yellow dye offormula (102) and 0.46 part of the blue dye of formula (103), using thereactive dyes indicated in column 2 of the following Table 1 in theamounts specified therein, there are likewise obtained brown dyeingsthat are distinguished by good levelness and good fastness properties.TABLE 1 Ex. Dye 2 0.45 part of the red dye of formula (101), 0.40 partof the blue dye of formula (103) and 0.70 part of the yellow dye offormula

(104) 3 0.45 part of the red dye of formula (101), 0.40 part of the bluedye of formula (103) and 0.42 part of the yellow dye of formula (105)

Method Example 3

[0117] 100 kg of texturised polyamide 6.6 tricot are treated in a dyeingapparatus for 10 min. at 40° C. with 2000 l of liquor containing 4 kg ofacetic acid, 0.5 kg of wetting agent and 1 kg of a levelling agent. ThepH of the liquor is 3.4. Subsequently, 430 g of the dye of formula(102), 300 g of the dye of formula (101) and 330 g of the dye of formula(103), predissolved in a small amount of water, are added.

[0118] The material to be dyed is treated for 5 min. at 40° C. in thedyeing liquor and then heated to 98° C. at a rate of 1° C./min. and dyedat that temperature for 60 min. The dyeing is finished in the usualmanner. A level dyeing having very good fastness properties is obtained

Method Example 4

[0119] 70 kg of a woven fabric of polyamide 6.6 microfibres are treatedin a dyeing apparatus for 10 min. at 40° C. with 1500 l of liquorcontaining 3 kg of formic acid, 0.4 kg of wetting agent and 0.7 kg of alevelling agent. The pH of the liquor is 2.9. Subsequently, 700 g of thedye of formula (102), 1300 g of the dye of formula (101) and 430 g ofthe dye of formula (103), predissolved in a small amount of water, areadded. The material to be dyed is treated for 5 min. at 40° C. in thedyeing liquor and then heated to 110° C. at a rate of 1° C./min. anddyed at that temperature for 60 min. After the dyeing, an alkalineaftertreatment is carried out to improve fastness to wetting properties.For that purpose, using a fresh bath containing 2 g/l of sodiumcarbonate and having a pH of 9.2, the dyeing is treated for 20 min. at60° C. The dyeing is then rinsed and finished in the usual manner. Alevel dyeing having excellent fastness properties is obtained.

Method Example 5

[0120] The procedure is as described in Method Example 4, except thatthe alkaline aftertreatment is carried out at 70° C. instead of at 60°C.

Method Example 6

[0121] The procedure is as described in Method Example 4, except thatthe alkaline aftertreatment is carried out in a bath containing 5 g/l ofsodium carbonate and 5 g/l of hydrosulfite. The dyeing is treated withthat bath for 20 min. at 70° C.

Method Example 7 (Space Dyeing)

[0122] A carpet of polyamide 6 yarn is first of all pad-dyed with aliquor containing, per 1000 parts of liquor, the following components:

[0123] 0.01 part of the yellow dye of formula (102)

[0124] 0.003 part of the red dye of formula (101),

[0125] 0.008 part of the blue dye of formula (103),

[0126] 3.00 parts of a customary commercial thickener,

[0127] 2.00 parts of a customary commercial non-ionic wetting agent,

[0128] 1.00 part of a customary commercial antifreeze, the pH beingadjusted to 5 using the required amount of citric acid.

[0129] Parts of the dyed carpet are then printed with a printing pastecontaining, per 1000 parts of printing paste, the following components:

[0130] 0.50 part of the red dye of formula (101),

[0131] 0.50 part of the blue dye of formula (103),

[0132] 15.0 parts of a customary commercial thickener,

[0133] 2.00 parts of a customary commercial non-ionic wetting agent,

[0134] 1.00 part of a customary commercial antifreeze,

[0135] the pH being adjusted to 5 using the required amount of citricacid The dyed and partially printed carpet is then treated withsaturated steam for 5 minutes at 100° C., washed in customary manner anddried. The carpet so obtained has, on a beige-coloured ground,red-printed areas which are distinguished by good levelness with goodfastness properties.

Method Example 8 (Continuous Dyeing)

[0136] A carpet of polyamide 6.6 yarn is dyed continuously with a liquorcontaining, per 1000 parts of liquor, the following components:

[0137] 0.8 part of the yellow dye of formula (102)

[0138] 0.28 part of the red dye of formula (101),

[0139] 0.46 part of the blue dye of formula (103),

[0140] 1.00 part of a customary commercial thickener,

[0141] 1.00 part of a customary commercial non-ionic wetting agent,

[0142] 3.00 parts of a customary commercial antifreeze,

[0143] the pH being adjusted to 5.5 using the required amount of citricacid. The dyed carpet fabric is then treated with saturated steam for 5minutes at 100° C., washed in customary manner and dried. The carpetobtained in that manner is distinguished by a level dark-brown dyeinghaving very good fastness properties.

Method Example 9 (Displacement Printing)

[0144] A carpet of polyamide 6.6 yarn is first of all printed withvarious printing pastes containing the following components, some ofwhich are in varying amounts x, y and z:

[0145] x parts of Tectilone® yellow 3R (Ciba Specialty Chemicals),

[0146] y parts of Tectilon® red 2B (Ciba Specialty Chemicals),

[0147] z parts of Tectilone® blue 4R-01 (Ciba Specialty Chemicals),

[0148] for example x is 1.05, y is 0.34 and z is 1.01,

[0149] 15.0 parts of a customary commercial thickener,

[0150] 10.0 parts of Lyoprint® MP

[0151] 2.00 parts of a customary commercial non-ionic wetting agent,

[0152] 1.00 part of a customary commercial antifreeze,

[0153] the pH being adjusted to 4 using the required amount of citricacid.

[0154] The printed carpet is then dyed with a liquor containing, per1000 parts of liquor, the following components (the liquor pick-up is350%):

[0155] 1.26 parts of the yellow dye of formula (102)

[0156] 0.62 part of the red dye of formula (101),

[0157] 1.90 parts of the blue dye of formula (103),

[0158] 1.00 part of a customary commercial thickener,

[0159] 2.00 parts of a customary commercial non-ionic wetting agent,

[0160] 2.00 parts of a customary commercial antifreeze,

[0161] the pH being adjusted to 5.5 using the required amount of citricacid.

[0162] The carpet is then treated with saturated steam for 5 minutes at100° C., washed in customary manner and dried. The carpet so obtainedhas, on a dark-violet ground, coloured areas which are distinguished bygood levelness with good fastness properties.

What is claimed is
 1. A method for the trichromatic dyeing or printingof synthetic polyamide fibre material, in which at least one redreactive dye of formula

is used together with at least one of the yellow or orange reactive dyesof formulae

and at least one blue reactive dye of formula

 in which formulae R₁, R₄, R₆, R₁₀, R₁₅ and R₁₆ are each independentlyof the others hydrogen, or C₁-C₄alkyl unsubstituted or substituted byhydroxy, sulfo, sulfato, carboxy or by cyano, R₂, R₅, R₇, R₁₃ and R₁₄are each independently of the others hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, ureido, sulfamoyl, halogen, sulfo or carboxy, R₃ isamino or N-mono- or N,N-di-C₁-C₄alkylamino, R₈ is hydrogen, sulfomethyl,carbamoyl or cyano, R₉ is C₁-C₄alkyl, R₁₁, and R₁₂ are eachindependently of the other hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, halogen,sulfo or carboxy, B is a C₂-C₆alkylene radical, which may be interruptedby 1, 2 or 3—O— members and which is unsubstituted or substituted byhydroxy or by sulfato, or a cyclohexylene radical ormethylene-cyclohexylene radical each of which is unsubstituted orsubstituted by C₁-C₄alkyl, or a phenylene ormethylene-phenylene-methylene radical each of which is unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or by sulfo, I is thenumber 0 or 1, k is the number 1, 2 or 3, and V₁ is a radical of formula

 in which formulae R₁₇ and R₁₉ are each independently of the otherhydrogen, or C₁-C₄alkyl unsubstituted or substituted by hydroxy, sulfo,sulfato, carboxy or by cyano, R₁₈ is C₁-C₄alkyl, C₁-C₄alkoxy, halogen orsulfo, Z is the radical —CH═CH₂ or —CH₂—CH₂—Y and Y is a leaving group,m is the number 0, 1 or 2, n is the number 0 or 1, and V₂, V₃, V₄ und V₅are each independently of the others a radical of the above-indicatedformula (6a), (6b), (6c) or (6d) or a radical of formula

 wherein R₂₀ is hydrogen, or C₁-C₄alkyl unsubstituted or substituted byhydroxy, sulfo, sulfato, carboxy or by cyano, and X is a radical

 and Hal is bromine or chlorine, with the proviso that the dye offormula (1) contains two sulfo groups.
 2. A method according to claim 1,wherein R₁, R₄, R₆, R₁₀, R₁₅, R₁₆, R₁₇, R₁₉ and R₂₀ are each hydrogen.3. A method according to claim 1, wherein R₂, R₅, R₇, R₁₃ and R₁₄ areeach independently of the others hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, ureido, sulfo or carboxy, and R₁₁ and R₁₂ are eachindependently of the other hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or sulfo.4. A method according to claim 1, wherein R₈ is hydrogen, sulfomethyl orcarbamoyl.
 5. A method according to claim 1, wherein B is aC₂-C₆alkylene radical, a methylene-cyclohexylene radical unsubstitutedor substituted by C₁-C₄alkyl, or a phenylene ormethylene-phenylene-methylene radical each of which is unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or by sulfo.
 6. A methodaccording to claim 1, wherein B is a radical of formula


7. A method according to claim 1, wherein I is the number
 0. 8. A methodaccording to claim 1, wherein V₁, V₂, V₃, V₄ and V₅ are eachindependently of the others a radical of formula (6c) or (6d) in whichR₁₇, R₁₈, R₁₉, Z, m and n are as defined in claim
 1. 9. A methodaccording to claim 1, wherein m is the number
 0. 10. A method accordingto claim 1, wherein n is the number
 0. 11. A method according to claim1, wherein R₁ is hydrogen, R₂ is sulfo, R₃ is amino, I is the number 0,and V₁ is a radical of formula (6c) in which R₁₇ is hydrogen, Z is vinyland m is the number
 0. 12. A method according to claim 1, wherein thereactive dye of formula (1) is a reactive dye


13. A method according to claim 1, wherein an aftertreatment is carriedout at a pH value of from 7 to 12 and a temperature of from 30 to 100°C.
 14. A method according to claim 13, wherein a reducing agent is addedto the aftertreatment bath.
 15. A reactive dye of formula

wherein R₁ and R₁₇ are each independently of the other hydrogen, orC₁-C₄alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato,carboxy or by cyano and Z is the radical —CH═CH₂ or —CH₂—CH₂—Y and Y isa leaving group.
 16. A process for dyeing or printing natural orsynthetic polyamide fibre material, which comprises applying to saidfibre material a reactive dye of formula (1b) according to claim
 15. 17.A process according to claim 16, for dyeing or printing syntheticpolyamide fibre material.